Fused 6,6,6-membered heterocyclic electroactive polymers

Abstract

Tractable doped electroactive polymers are fabricated from the virgin polymer by contacting the polymer with acceptor conductivity modifier atoms or groups of atoms. The polymers comprise recurring units of a fused unsaturated 6,6,6-membered heterocyclic ring systems wherein two heteroatoms are in the center ring and the recurring units are connected between the carbocyclic rings.

What is claimed is: 
     
       1. A p-type electroactive polymer which comprises a charge polymer backbone of recurring units of a fused 6,6,6-membered unsaturated heterocyclic ring system wherein 6,6,6-membered unsaturated heterocyclic ring system connects into the polymer backbone through bonding in the outer carbocyclic rings, the central 6-member ring contains two heteroatoms para to each other, said heteroatoms selected from the group consisting of O, S, N, and substituted N, and a sufficient concentration of a charge-compensating anionic conductivity modifier associated therewith, wherein the polymer backbone is capable of undergoing reversible oxidation to form said charged polymer backbone. 
     
     
       2. The electroactive polymer according to claim 1 wherein the recurring units are selected from the group consisting of phenoxazine; N-alkyl phenoxazine; phenothiozine, thianthrene; phenoxathiin; dialkyldihydrophenazine; dihydrophenazine; dibenzodiozin; substituted derivatives thereof, wherin said substituted derivatives thereof are said recurring units substituted with from 1 to 3 substituents on the outer carbocyclic rings independently selected from H; disubstituted amino; alkyl of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms; alkylthio of 1 to 4 carbon atoms; a cycloaliphatic group of 5 or 6 carbon atoms; an aryl group of 6 to 10 carbon atoms; an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthio of 1 to 4 carbon atoms; and a 5- or 6-membered nitrogen-containing unsaturated heterocyclic ring; and mixtures thereof. 
     
     
       3. The electroactive polymer according to claim 2 wherein the recurring units are linked into the polymer chain in the 2,7; 2,8; 3,7; or 3,8 positions. 
     
     
       4. The electroactive polymer according to claim 3 wherein the charge-compensating ionic dopant is an anion selected from the group consisting of AsF 4   - , AsF 6   - , ClO 4   - , PF 6   - , SO 3  CF 3   - , BF 4   - , NO 3   - , POF 4   - , CN - , SiF 5   - , SbCl 6   - , SbF 6   - , HSO 4   - , acetate, benzoate, tosylate, or mixtures thereof. 
     
     
       5. The electroactive polymer according to claim 3 wherein the recurring units are interspersed with connecting units, said connecting unit is selected from the group consisting of ##STR15## wherein R 1  is lower alkyl C 1  -C 6 , and cyclo alkyl, and R v , R vi  and R vii  are H, methyl, methoxy, halogen, and mixtures thereof. 
     
     
       6. The electroactive polymer according to claim 5 wherein the fused 6,6,6-membered heterocyclic recurring units are interspersed with connecting units selected from the group consisting of phenylene, dithiophenylene --CH═CH--, biphenylene, dithiobiphenylene, and ##STR16## or mixtures thereof. 
     
     
       7. The electroactive polymer according to claim 6 or 3 wherein the recurring unit is phenoxathiin. 
     
     
       8. The electroactive polymer according to claim 7 wherein the polymer is poly 3,7-(phenoxathiin-4,4'-dithiobiphenylene) plus a charge compensating anionic dopant. 
     
     
       9. The electroactive polymer according to claim 6 or 3 wherein the recurring unit is phenothiazine. 
     
     
       10. The electroactive polymer according to claim 9 wherein the polymer is poly 3,7-(N-methyl phenothiazine-2,5-oxadiazole) plus a charge compensating anionic dopant. 
     
     
       11. The electroactive polymer according to claim 10 or 3 wherein the charge-compensating ionic dopant is an anion selected from the group consisting of AsF 4   - , AsF 6   - , ClO 4   - , PF 6   - , SO 3  CF 3   - , BF 4   - , NO 3   - , POF 4   - , CN - , SiF 5   - , SbCl 6   - , SbF 6   - , HSO 4   - , acetate, benzoate, tosylate, or mixtures thereof. 
     
     
       12. A p-type electroactive polymer which comprises a charged polymer backbone and charge-compensating ionicdopants associated therewith of the formula:   --R--X'--.sub.a --R'--.sub.c --Y'--.sub.b --.sub.n .sup.(+Sd) [M.sup.-S ].sub.d     wherein a is 0 or 1; b is 0 or 1; c is 0 or 1; n is an integer from 1 to 1,000; d is an integer from 1 to 2,000; s is an integer 1, 2, or 3; R is a fused 6,6,6-membered unsaturated diradical-heterocyclic ring system wherein two heteroatoms are para in the central 6-membered ring and the heteroatoms are selected from the group consisting of O, S, N, N--R 1  wherein R 1  is lower alkyl C 1  -C 6 , aryl and cycloalkyl; R' is the same as R or a different fused 6,6,6-membered unsaturated heterocyclic ring system; X' is a connecting unit; Y' is the same connecting unit as X' or a different connecting unit; and M is a charge-compensating anionic dopant of opposite electrical charge to the charge of the polymer backbone wherein an X' or Y' connecting unit is selected from the group consisting of: ##STR17## wherein R 1  is lower alkyl C 1  --C 6  , aryl and cyclo alkyl, and R v , R vi  and R vii  are H, methyl, methoxy, halogen and mixtures thereof.   
     
     
       13. The electroactive polymer according to claim 12 wherein R and R' are diradicals of the formula: ##STR18## wherein X and Y are independently selected from the group consisting of substituted N, O, S, N--R 1  ; wherein R 1  is lower alkyl C 1  -C 6 , areyl, cyclo alkyl; R ii  and R iii  are from one to three substituent groups independently selected from H; disubstituted amino; alkyl of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms; an alkylthio of 1 to 4 carbon atoms; a cycloaliphatic group of 5 to 6 carbon atoms; an aryl group of 6 to 10 carbon atoms; an aryl group of 6 to 10 carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen atoms, dialkyl amino groups of 1 to 4 carbon atoms, an alkylthiol 1 to 4 carbon atoms; a 5- or 6-member nitrogen-containing unsaturated heterocyclic group. 
     
     
       14. The electroactive polymer according to claim 13 wherein a, b and c are zero, and the polymer has the formula:   --R--.sub.n.sup.(+Sd) [M.sup.-S ].sub.d     
     
     
       15. The electroactive polymer according to claim 12 or 13 wherein a is 1, b and c are zero, and the polymer has the formula:   --R--X'--.sub.n.sup.(+Sd) [M.sup.-S ].sub.d     
     
     
       16. The electroactive polymer according to claim 15 wherein X and Y are O and S for the diradical R. 
     
     
       17. The electroactive polymer according to claim 15 where X and Y are N--R 1  and S for the diradical R. 
     
     
       18. The electroactive polymer according to claim 17 wherein X is S, Y is N--R 1 , and R 1  is CH 3  for the diradical R and X' is ##STR19## and the polymer has the formula: ##STR20## 
     
     
       19. The electroactive polymer according to claim 18 wherein the charge-compensating ionic dopant M is an anion selected from the group consisting of AsF 4   - , AsF 6   - , ClO 4   - , PF 6   - , SO 3  CF 3   - , BF 4   - , NO 3   - , POF 4   - , CN - , SiF 5   - , SbCl 6   - , SbF 6   - , HSO 4   - , acetate, benzoate, tosylate, F - , Cl - , or mixtures thereof. 
     
     
       20. The polymer poly-3,7-(N-methylphenothiazine)-2,5-(1,3,4-oxadiazole).